9-Allyl-3,6-dibromo-9H-carbazole

The title compound, C₁₅H₁₁Br₂N, was synthesized by N-alkyl­ation of 3-bromo­propene with 3,6-dibromo-9H-carbazole. The carbazole ring system is essentially planar and perpendicular to the pendant allyl substituent.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.005 Å
• R factor = 0.035
• wR factor = 0.088
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

S1. Comment

Carbazole derivatives substituted by N-alkylation possess valuable pharmaceutical properties (Buu-Hoï & Royer, 1950; Harfenist & Joyner, 1983; Caulfield et al., 2002; Harper et al., 2002). In this paper, the structure of 9-allyl-3,6-dibromo-9H-carbazole, (I), is reported. It was synthesized by N-alkylation of 3-bromo-propene with 3,6-dibromo-9H-carbazole. The carbazole ring is essentially planar, with a mean deviation of 0.0082 Å from the plane, consistent with recent determinations of similar structures (Huang et al., 2005; Duan, Han et al., 2005 or Duan, Huang et al., 2005). The angle between the carbazole ring and the plane of the allyl is 89.8 (3)°. The C—Br distances are in the range 1.908 (4)–1.910 (4) Å, consistent with the literature (Allen et al., 1987).

S2. Experimental

The title compound, (I), was prepared as described by Duan, Han et al. (2005) or Duan, Huang et al. (2005). A solution of potassium hydroxide (7.0 g) in dimethylformamide (50 ml) was stirred at room temperature for 20 min. 3,6-Dibromocarbazole (6.5 g, 20 mmol), prepared as in Smith et al. (1992), was added and the mixture stirred for a further 40 min. A solution of 3-bromopropene (3.63 g, 30 mmol) in dimethylformamide (50 ml) was added dropwise with stirring. The resulting mixture was then stirred at room temperature for 12 h and poured into water (500 ml), yielding a white precipitate. The solid product was filtered off, washed with cold water and recrystallized from EtOH, giving crystals of (I) (yield 6.53 g, 89.5%; m.p. 376–378 K). Compound (I) (40 mg) was dissolved in mixture of chloroform (5 ml) and ethanol (5 ml) and the solution was kept at room temperature for 16 d. Natural evaporation of the solution gave colourless crystals suitable for X-ray analysis.

S3. Refinement

All H atoms were included in the riding-model approximation, with C—H = 0.93 (aromatic) and 0.97 Å (methylene), and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

9-Allyl-3,6-dibromo-9H-carbazole

Crystal data

C15H11Br2N	F(000) = 712
Mr = 365.07	Dx = 1.778 Mg m^−3
Monoclinic, P21/c	Melting point: 377(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.6763 (12) Å	Cell parameters from 2800 reflections
b = 10.6439 (15) Å	θ = 3.0–25.2°
c = 15.7934 (18) Å	µ = 5.93 mm^−1
β = 110.803 (6)°	T = 294 K
V = 1363.4 (3) Å^3	Rod, colourless
Z = 4	0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2837 independent reflections
Radiation source: fine-focus sealed tube	2088 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 26.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→8
Tmin = 0.228, Tmax = 0.306	k = −11→13
7598 measured reflections	l = −19→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 0.9467P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2837 reflections	Δρmax = 0.39 e Å^−3
164 parameters	Δρmin = −0.44 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0155 (9)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.55897 (5)	0.57224 (4)	0.37589 (3)	0.07437 (18)
Br2	0.32089 (6)	0.22977 (4)	−0.15446 (3)	0.0791 (2)
N1	0.0904 (3)	0.6775 (3)	−0.0007 (2)	0.0524 (7)
C1	0.2938 (4)	0.5632 (3)	0.1008 (2)	0.0449 (7)
C2	0.4035 (4)	0.5330 (3)	0.1871 (2)	0.0504 (8)
H2	0.4734	0.4640	0.1964	0.061*
C3	0.4048 (4)	0.6086 (3)	0.2578 (2)	0.0537 (9)
C4	0.3024 (5)	0.7121 (3)	0.2466 (3)	0.0575 (9)
H4	0.3078	0.7608	0.2965	0.069*
C5	0.1934 (5)	0.7428 (3)	0.1627 (3)	0.0584 (9)
H5	0.1241	0.8120	0.1547	0.070*
C6	0.1882 (4)	0.6685 (3)	0.0895 (2)	0.0472 (8)
C7	0.1318 (4)	0.5825 (3)	−0.0485 (2)	0.0497 (8)
C8	0.0674 (5)	0.5550 (4)	−0.1403 (3)	0.0617 (10)
H8	−0.0135	0.6053	−0.1804	0.074*
C9	0.1271 (5)	0.4511 (4)	−0.1701 (3)	0.0652 (10)
H9	0.0848	0.4298	−0.2312	0.078*
C10	0.2498 (5)	0.3773 (3)	−0.1102 (3)	0.0558 (9)
C11	0.3175 (4)	0.4043 (3)	−0.0198 (2)	0.0496 (8)
H11	0.4009	0.3546	0.0191	0.060*
C12	0.2576 (4)	0.5086 (3)	0.0124 (2)	0.0461 (8)
C13	−0.0349 (4)	0.7725 (3)	−0.0404 (3)	0.0587 (9)
H13A	−0.0819	0.7977	0.0042	0.070*
H13B	−0.1226	0.7357	−0.0912	0.070*
C14	0.0284 (5)	0.8864 (3)	−0.0725 (2)	0.0551 (9)
H14	−0.0476	0.9492	−0.0996	0.066*
C15	0.1788 (6)	0.9059 (4)	−0.0662 (3)	0.0701 (11)
H15A	0.2592	0.8457	−0.0397	0.084*
H15B	0.2069	0.9801	−0.0882	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0609 (3)	0.0888 (3)	0.0620 (3)	−0.0164 (2)	0.00785 (19)	−0.0021 (2)
Br2	0.1070 (4)	0.0533 (2)	0.0971 (4)	−0.0174 (2)	0.0610 (3)	−0.0169 (2)
N1	0.0500 (16)	0.0420 (15)	0.0663 (19)	0.0070 (12)	0.0219 (15)	0.0134 (14)
C1	0.0424 (17)	0.0373 (16)	0.056 (2)	−0.0046 (14)	0.0195 (15)	0.0045 (14)
C2	0.0418 (18)	0.0414 (17)	0.066 (2)	−0.0027 (14)	0.0165 (17)	0.0070 (16)
C3	0.051 (2)	0.054 (2)	0.056 (2)	−0.0160 (16)	0.0194 (17)	−0.0007 (17)
C4	0.065 (2)	0.046 (2)	0.069 (2)	−0.0105 (17)	0.033 (2)	−0.0083 (18)
C5	0.064 (2)	0.0413 (19)	0.078 (3)	0.0032 (16)	0.035 (2)	0.0055 (17)
C6	0.0464 (18)	0.0391 (17)	0.060 (2)	−0.0036 (14)	0.0232 (16)	0.0079 (15)
C7	0.0480 (19)	0.0433 (18)	0.059 (2)	−0.0041 (15)	0.0208 (16)	0.0118 (16)
C8	0.063 (2)	0.059 (2)	0.061 (2)	−0.0001 (18)	0.0194 (19)	0.0163 (18)
C9	0.076 (3)	0.064 (2)	0.057 (2)	−0.018 (2)	0.026 (2)	0.0017 (19)
C10	0.067 (2)	0.0443 (19)	0.066 (2)	−0.0148 (17)	0.036 (2)	−0.0034 (17)
C11	0.0491 (19)	0.0399 (17)	0.063 (2)	−0.0048 (14)	0.0239 (17)	0.0056 (16)
C12	0.0452 (18)	0.0381 (16)	0.058 (2)	−0.0049 (14)	0.0224 (16)	0.0055 (15)
C13	0.052 (2)	0.053 (2)	0.073 (2)	0.0112 (16)	0.0252 (19)	0.0173 (18)
C14	0.068 (2)	0.0454 (19)	0.056 (2)	0.0096 (17)	0.0280 (18)	0.0111 (16)
C15	0.091 (3)	0.055 (2)	0.079 (3)	−0.011 (2)	0.048 (2)	0.0010 (19)

Geometric parameters (Å, º)

Br1—C3	1.910 (4)	C7—C12	1.410 (5)
Br2—C10	1.908 (4)	C8—C9	1.373 (5)
N1—C6	1.378 (4)	C8—H8	0.9300
N1—C7	1.383 (4)	C9—C10	1.389 (6)
N1—C13	1.454 (4)	C9—H9	0.9300
C1—C2	1.395 (5)	C10—C11	1.368 (5)
C1—C6	1.418 (4)	C11—C12	1.396 (5)
C1—C12	1.440 (5)	C11—H11	0.9300
C2—C3	1.373 (5)	C13—C14	1.492 (5)
C2—H2	0.9300	C13—H13A	0.9700
C3—C4	1.387 (5)	C13—H13B	0.9700
C4—C5	1.367 (5)	C14—C15	1.290 (5)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.388 (5)	C15—H15A	0.9300
C5—H5	0.9300	C15—H15B	0.9300
C7—C8	1.388 (5)
C6—N1—C7	109.2 (3)	C7—C8—H8	121.1
C6—N1—C13	125.8 (3)	C8—C9—C10	120.9 (4)
C7—N1—C13	124.9 (3)	C8—C9—H9	119.6
C2—C1—C6	119.4 (3)	C10—C9—H9	119.6
C2—C1—C12	133.8 (3)	C11—C10—C9	122.2 (4)
C6—C1—C12	106.8 (3)	C11—C10—Br2	118.7 (3)
C3—C2—C1	117.7 (3)	C9—C10—Br2	119.0 (3)
C3—C2—H2	121.1	C10—C11—C12	118.0 (3)
C1—C2—H2	121.1	C10—C11—H11	121.0
C2—C3—C4	122.9 (3)	C12—C11—H11	121.0
C2—C3—Br1	118.4 (3)	C11—C12—C7	119.6 (3)
C4—C3—Br1	118.7 (3)	C11—C12—C1	133.9 (3)
C5—C4—C3	120.3 (3)	C7—C12—C1	106.6 (3)
C5—C4—H4	119.9	N1—C13—C14	113.7 (3)
C3—C4—H4	119.9	N1—C13—H13A	108.8
C4—C5—C6	118.6 (3)	C14—C13—H13A	108.8
C4—C5—H5	120.7	N1—C13—H13B	108.8
C6—C5—H5	120.7	C14—C13—H13B	108.8
N1—C6—C5	130.3 (3)	H13A—C13—H13B	107.7
N1—C6—C1	108.5 (3)	C15—C14—C13	126.1 (3)
C5—C6—C1	121.1 (3)	C15—C14—H14	117.0
N1—C7—C8	129.6 (3)	C13—C14—H14	117.0
N1—C7—C12	108.9 (3)	C14—C15—H15A	120.0
C8—C7—C12	121.5 (3)	C14—C15—H15B	120.0
C9—C8—C7	117.8 (3)	H15A—C15—H15B	120.0
C9—C8—H8	121.1
C6—C1—C2—C3	−0.5 (4)	N1—C7—C8—C9	−177.5 (3)
C12—C1—C2—C3	179.7 (3)	C12—C7—C8—C9	1.7 (5)
C1—C2—C3—C4	0.1 (5)	C7—C8—C9—C10	−1.0 (5)
C1—C2—C3—Br1	−178.0 (2)	C8—C9—C10—C11	−0.4 (6)
C2—C3—C4—C5	0.2 (5)	C8—C9—C10—Br2	177.2 (3)
Br1—C3—C4—C5	178.4 (3)	C9—C10—C11—C12	1.1 (5)
C3—C4—C5—C6	−0.1 (5)	Br2—C10—C11—C12	−176.5 (2)
C7—N1—C6—C5	179.3 (3)	C10—C11—C12—C7	−0.4 (5)
C13—N1—C6—C5	0.3 (5)	C10—C11—C12—C1	178.1 (3)
C7—N1—C6—C1	−1.2 (3)	N1—C7—C12—C11	178.4 (3)
C13—N1—C6—C1	179.8 (3)	C8—C7—C12—C11	−1.0 (5)
C4—C5—C6—N1	179.2 (3)	N1—C7—C12—C1	−0.5 (3)
C4—C5—C6—C1	−0.3 (5)	C8—C7—C12—C1	−179.9 (3)
C2—C1—C6—N1	−178.9 (3)	C2—C1—C12—C11	0.8 (6)
C12—C1—C6—N1	0.9 (3)	C6—C1—C12—C11	−178.9 (3)
C2—C1—C6—C5	0.6 (5)	C2—C1—C12—C7	179.5 (3)
C12—C1—C6—C5	−179.6 (3)	C6—C1—C12—C7	−0.2 (3)
C6—N1—C7—C8	−179.6 (3)	C6—N1—C13—C14	90.4 (4)
C13—N1—C7—C8	−0.6 (5)	C7—N1—C13—C14	−88.5 (4)
C6—N1—C7—C12	1.1 (4)	N1—C13—C14—C15	−1.2 (6)
C13—N1—C7—C12	−179.9 (3)